Separation of amines by urea complex formation



E. GORIN SEPARATION OF AMINES BY UREA COMPLEX FORMATION Filed Sept. 13. 1949 2 Shee'ts-Sheet l fere an'n/ INVENToR.

ABY

June 15, 1954 E, GOR|N 2,681,332

SEPARATION OF AMINES BY UREA COMPLEX FORMATION Filed sept. 15, 194e 2 sheets-sheet 2 cfm/M5 l (Hwa z-t/aolra-N-atmmwvas) 5 i@ soz vf/v REN/mv f6 50i VENT C//RGE T11/fao une@ cms/r INVENzoR. Everl ann/ Patented June 15, 1954 TENT OFFICE SEPARATION OF AMINES BY UREA COMPLEX FORMATION Everett Gorin,

Castle Shannon, Pa., Socony-Vacuum Oil Company, corporation of New York assignor to Incorporated, a

Application September 13, 1949, Serial No. 115,515

2 Claims.

This invention has to do with the separation of hydrocarbons and hydrocarbon derivatives of different molecular configuration from mixtures containing the same, and also has to do with the preparation of new and novel compositions.

I. FIELD OF INVENTION Numerous processes have been developed for the separation of hydrocarbons and hydrocarbon derivatives of different molecular configuration by taking advantage of their selective solubility in selected reagents or solvents from which they may later be separated. Exemplary of hydrocarbon separation procedures is the Edeleanu process, wherein parafnic materials are separated from aromatics by Virtue of the greater solubility of aromatics in liquid sulfur dioxide. Lubricant oil solvent rening processes, solvent deasphalting, solvent dewaxing and the like are further examples of the separation of hydrocarbons of different molecular conguration. Typical of selective solvent procedures for separating hydrocarbon derivatives is the separation of paraflin wax, monochlorwax and polychlorwaxes, with acetone as the selective solvent.

This invention is concerned with the general iield outlined above, but based upon a different and little-known phenomenon, namely, the differing ability of hydrocarbons and hydrocarbon derivatives to enter certain crystalline complexes. As used herein, the term complex broadly denotes a combination of two or more compounds.

This invention is predicated upon the knowledge that urea forms complex crystalline compounds to a varying degree with various forms of hydrocarbons and hydrocarbon derivatives.

II. PRIOR ART For some years it has been known that various .isomers of aromatic hydrocarbon derivatives into and to be removed from ant (Priewe-1,933,757). Bentley and Catlow (1,980,991) found a number of aromatic amines containing at least one basic amino group capable of forming double compounds with certain isomeric phenols. It has also been shown that trans-oestradiol can be separated from the corresponding cis-compound by forming a dircultly soluble compound of urea and trans-oestradiol (Priewe-2,30l,134)

rhe forces between urea and the compounds of the foregoing complexes are due to speoic chemical interaction between the various functional groups.

One heteroeyclic compound, 2:6 lutidine, has been found to form a crystalline compound with urea, thus aiording a means of separating the lutidine from betaand gamma-picolines (Riethof--2,295,606)

Comparatively few aliphatic hydrocarbon derivatives have been known to date to form complex compounds with urea. In German patent application B190,l97, ivd/12 (Technical Oil Mission, Reel 143,' Library of Congress, May 22, 1946), Bengen described a method for the sepa- Y ration of aliphatic oxygen-containing compounds (acids, alcohols, aldehydes, esters and ketones) and of straight chain hydrocarbons of at least six carbon atoms from mixtures containing the same, the method being predicated upon the ability of such compounds and hydrocarbons to form Additions-Produkt with urea. In the Technical Oil Mission translation of the Bengen application, however, the urea complexes were designated adducts which term apparently stems from the anglicized addition product.

III. DEFINITIONS From the foregoing discussion of prior art (II), it will be clear that a variety of terms have been applied to urea complexes. The latter have been rather loosely described as double compounds, addition compounds, dicultly soluble compounds, Additions-Produkt, and adducts All of these terms are somewhat ambiguous in that they have also been used to describe products or complexes of different character than the urea complexes under consideration. This is particularly so with the term adduct, and the related term unadducted material. While the term adduct is simple and convenient, it is an unfortunate designation, inasmuch as it confuses these complexes with other substances known in the chemical art. Specifically, adduct has been applied to Diele-Alder reaction products, formed by reaction of conjugated dioleins and olelns and their derivatives. As is well known, Diels-Alder products, as a rule do not revert to their original constituents when heated or treated with water, acids, solvents, etc. Moreover, the term adduct has been defined earlier as the product of a reaction between molecules, which occurs in such a way that the original molecules or their residues have their long axes parallel to one another. (Concise Chemical and Technical Dictionary.) Further ambiguity is introduced by the term vadduction, which has been defined as oxidation (Hackh.) f

To avoid the foregoing connicting terminology, several related terms have beenV coined to denne with greater speciiicity the substances involved in the phenomenon under consideration. As contemplated herein and as used throughout the specification and appended claims, the following terms identify the phenomenon:

VPlexad-a revertible associated complex comprising a plexor, such as urea, and at least one other compound; said plexad characterized by reverting or decomposing, under the influence of heat and/or various solvents, to its original constituents, namely, a plexor and yat least one plexand.

Plexand-a compound capable of forming a plexad with a plexor, such as urea; compounds of this character diier in their capacity to form plexads, depending upon various factors described hereinafter.

Y nntiplex-a compound incapable of forming a plexad with a plexor.

Plexor-a compound capable of forming a plexad with a plexand; such as urea.

Plexate-to form a plexad.

Plexation-the act, process or effect of plexating.

IV. OUTLINE OF INVENTION non-terminal substituents'are different, and the number of carbon atoms of the substituted paraiilns are the same or different` rI'he substituent groups which may characterize the terminally-substituted compounds are inorganic and organic groups oi the following character:

(c) Halogen:

F, Cl, Br and I; (b) Nitrogen-containing:

NH2, DTI-HR), NRz, NO2, NOH, CN, CONI-l2, CCNE-HR), CON R)2, CNO, CNS, NGO,

NCS, etc., wherein R is a hydrocarbonY radical; (c) Sulfur-containing:

SH, SR, SOzII, OSOSH, SOzH, SOzR, wherein Ris a hydrocarbon radical, ,SOZZ wherein Z is a halogen atom, etc.; (d) Cyclic:

cycloalkyl such as cyclopropyl, cyclobutyl,

cyclopentyl, cyclohexyl, cycloheptyl, chlorif cyclohexyl, etc.; aryl such as phenyl and chlorphenyl; hetero such as thienyl CiHsS, uryl (24H30, pyrryl Cil-14N, pyridyl (35i-14N, thiazyl Cal'lzNS, pyrazolyl CaHsNz, piperydyl Csi-RUN, etc.; (e) Alkenyl:

Methylene, Vinyl, etc.; (f) l-laloalkyl:

Dichlormethyl ClzCH-, etc.

As contemplated herein, the invention makes possible the separation oi one or more plexancls from a mixture containing the same, such plexand or plexands being separated in the form of a pleXa-d or plexads which, as described in detail hereinbelow, revert to the plexor, urea, and the plexand or plexands under certain conditions. The separation, therefore, is an excellent means for obtaining, in pure or concentrated form, one or more plexands or antiplexes whichever is the desired material. The invention also provides a means of forming new compositions oi matter, namely, a number of plexads which may be used as a source of a plexor, urea, or as a source of a plexand.

V. OBJECTS t is an object of this invention, therefore, to provide an effective means for separating hydrocarbons and hydrocarbon derivatives oi different molecular configuration from mixtures containing the same. Y

lt is also an object of this invention to selectively separate terminally-substituted straight chain compounds from mixtures containing the same. Y

A further object is to separate a terminallysubstituted straight chain compound from a mixture containing the same and a non-terminally substituted isomer.

Still another object is to separate a terminallysubstituted straight chain compound from a mixture containing the same and a non-terminallysubstituted straight chain compound having a different number oi carbon atoms.

An additional object is to separate a terminally-substituted straight chain compound'rom a non-terminally-substituted compound, wherein the substituents are diferent and the number of carbon atoms oi Vthe respective compounds are the saine. A related object is to separate a terminally-substituted straight chain compound from a nonterminally-substituted compound, wherein the substituents are different and the number of carbon atoms of the respective compounds are different.

A further object is to separate a non-terminally-substituted compound from a mixture containing the same and a second non-terminally-substituted compound less susceptible to plexation.

Another important object is the provision of a continuous method o separation of said plexands and antiplexes, which method is iiexible, capable of relatively sharp separation, and not highly demanding of attention and of utilities such asV heat, refrigeration, pumping power, and the like. An additional object is to provide a plexand or plexands substantially free of an antiplex v-or antiplexes. A oorresponding'object is the pro- Vision of an antiplex or antiplexes substantially free ci said plexand or plexands.

Another object is to provide a new and novel class or sub-classes of plexads comprising a plexand and urea. A related object is the provision of a new and novel class or sub-classes of plexads comprising a secondary plexand and urea;

5 l Other objects and advantages ci vthe invention will `be `apparent from the following description.

` VI. INVENTION IN DETAIL l As indicated above, it has been found that the foregoing objects are achieved by plexation with urea (a plexor) of a plexand or plexands.

(l) PLEXANns `Plexands contemplated herein are) represented by the general Formula A; (A) X(CH`2)CH3 wherein n is a whole number and wherein X is a substituent group of the above, with n and X being interrelated.

The substituent group X may be any of the' quantitative measure as the` distance from be tween outer covalent radii of the two most widely '30 separated atoms along the cross-section of the group where the lcovalent radii are those given by Pauling (Pauling-Nature of the Chemical Bond; Cornell University Press; Ithaca, N. Y.; 1939). The second distance-length-is the projection along the bond joining the group to `the parent hydrocarbon of the distance from the center of `the carbon atom to which the groupA is attached, to the center `ofithe atom whose covalent radius shell extends furthest in the di,-l rection of said bond, plus the covalent radius of said bond.

The rst distance determines the length of the aliphatic chain required to obtain plexation at room temperature (25 C.) with a saturated urea solution, a plexor, when the group (X) in question is attached to the terminal carbon atom of the aliphatic chain. In the case of composite groups of the type -COY, CH2COY and -CH2Y, where Y is a non-aliphatic radical such as chlorine or amino, the ICO, -CHQCO and -CHZ- constituents, respectively, are considered as part of the aliphatic chain andthe width" computed is that for the radical Y.

The widths of a number of typical groups computed according to the method are listed in order of size in Table I below:

TABLE L WIDTH `OFVARIOUS GROUPS IN A -ACN 1.20 -F 1.28 -Cl 1.98 -CHzCl 1.98 -NI-Iz 2.11 -CONI-Iz 2.11 -Br 2.28 M -I 2.66 -SH 2.67 NO2 3.32 '-,SOaI-I 3.69 Thienyl 4.38 Cyclohexyl 4.74 -Phenyl 5.15 2 or 3 methyl cyclohexyl 5.49 O or M-tolyl 6.09

The correlation betwenthe" Wi`dth`" "ofthe character described given abgv group and the length of the aliphatic chain required for '-pleXadformation at room temperature san approximate-one. This relationship depedsto some extent upon the nature of the group (X) as well as upon the width of the group (X). For example, in the case where two 'groups (X) are the same size, the group which imparts a higher melting point to the substituted paraffin will form `the stronger plexad, i. e., will form a pleXad when the aliphatic chain is` somewhat shorter in length.

Onlythe carbon atoms inthe chain are considered to contribute to the chain length, that is, atoms such as oxygen, sulfur, nitrogen, etc., are not included in the atom total. Accordingly, then, the straight chain compounds contemplated herein include straight chain aliphatic hydrocarbons and straight chain aliphatic hydrocarbons in which one or more of the carbon atoms of the chain have been replaced by such atoms as oxygen, sulfur, nitrogen, and the like.

It is possible, however, to give the unequivocal limits for Vthe relation between width of the group (X) and size of the carbon chain required for plexation with urea at room temperature, 25 C. These limits are set forth in rlable II below: l i

TABLE II.-CORRELATION BETWEEN WIDTH OF GROUP (X) AND MINIMUM CHAIN LENGTH FOR UREAPLEXATION AT 25 C. i

Minirnlun W d h Lohath t eng Group 1 Numb er of (m A') Carbon.V Atoms 4 It is to be understood that these limits apply for plexation at temperatures of the order o about 25 C. The minimum number of carbon atoms in the chain is generally lower for plexa* tion at lower temperatures, but generally not more than one or two carbon atoms lower. in the same vein, for an increase in temperature, a correspondingly higher number of carbon atoms will be required in the carbon chain.

By way of illustration, the following compounds are typical plexands:

(a) Halogen compounds:

n-Heptyl iluoride, n-heptyl' bromide, noctyl chloride, n-octyl bromide, n-hexadecyl chloride, n-hexadecyl bromide, n octadecyl chloride, n-octadecyl bromide; etc. (b) Nitrogen-containing compounds:

Aminon-Octylamine; n-decyl amine; n--hexadecyl amine; n-octadecyl amine; noctadecenyl amine; methyl, n-octy1 amine; butyl, n-octyl amine; etc. Cyano n-Hexyl nitrile; n-octyl nitrile; n-tetradecyl nitrile; n-octadecyl nitrile; etc. Nitro- 1nitrondecane; l-nitro-n-dodecane;

1nitronoctadecane; etc. Amidon Octanamide; n dodecanamide; n octadecanamide; n f octadecenamide; l `15T-methyl, n-actanamide; N-hexyl, n-

decanamide; etc.

lforegoing Cyanate and isocyanate n-I-Iexyl cyanate; n-hexyl isocyanate; n-decyl cyanate; n-decyl isocyanate; n-hexadecyl cyanate; n-hexadecyl isocyanate; etc. Thiocyanate and isothiocyanaten-Decyl thiocyanate; n-decyl isothiocyanate; n-octadecyl thiocyanate; noctadecyl isothiocyanate; etc. Sulfur-containing compounds: Mercapton-Octyl mercaptan; n-dodecyl mercaptan; n-hexadecyl mercaptan; noctadecenyl mercaptan; etc. Sulfido (SR)- Methyl, n-octyl suliide; butyl, n-dodecyl sulfide; amyl, n-heXadecyl sulde; etc. Sulfaton-Dodecyl sulfate; n-hexadecyl sulfate;

etc. Sulfonyl haliden-Decyl sulionyl chloride; n-dodecyl sulfonyl bromide; n-hexadecyl sulfonyl iodide; etc. Cyclic substituent: 1-cyclopropyl-n-octadecane; l-cyolohexyln-hexadeoane; l-phenyl-n-octadecane; 1- thienyl-n-octadecane; etc.

It is to be understood that terminally-substituted straight chain compounds containing a second terminal substituent on the opposite terminal carbon atom, are also contemplated herein as plexands. Such disubstituted compounds are also subject to approximately the relationships of terminal group width and chain length. Compounds of this character are represented by the following general formula:

wherein n is a the same or'diierent and as defined above.

Illustrative of such compounds are:

1,10-dichlor-n-decane; 1,8-n-octane diamine; 1,10-n-decane diamide; 1,12-n-dodecane dithiol; 1,l8disulfonoctadecane; etc.

wholenumber, and X and X' are (B) HQCHZMIZmoHnmCHB wherein r and m are integers, the sum of which p is equal to n-Z, and n and X are as dened above.

The length, rather than the width, o the substituent group (X) roughly determines the minimum carbon chain length required for plexation of the foregoing plexands (B) namely, non-terminally substituted straight chain compounds. These compounds may be consid ered secondary plexands. The minimum chain length is also. to some extent a function of the position substituted as well as of the chemical nature of the group. Thus, in compounds of this type, the minimum chain length required for plexation is determined by the length of groupV is small enough so that this alkyl group is shorter in length than the substituent group (X). It is possible, bearing this relationship in mind however, also to give rather wide limits in the correlation of group length with the minimum chain length required for plexation. The lengths of various groups are given in Table III, below, while the correlation TABLE IV.-CORRELATION BETWEEN LENGTH OF NON-TERMINALLY-SUB STITUTED GROUPS AND MIN- HUM. CHAIN LENGTH REQUIRED FOR UREA PLEX- ATION AT 25 C.

Minimum Chain Length, Number of Carbon Atoms Length 2-ohloro-n-tetracosane; y 2-bromo -n-tetracosane;

Y 2 -amino-n-decane;

2-nitro-n-octadecane; etc.

Considering the relationships shown by Tables III and IV, it will be` seen that 2-chloro-noctadecane, for example, will form a plexad with urea at about 25 C. This, then, illustrates a plexad comprising a secondary plexand and urea.

A further illustration is a non-terminal bromideY By way oi illustration, it follows from the foregoing that l-bromo-n-tetracosane is separated readily from a mixture of the same and an isomer such as Z-bromo-n-tetracosane. This is typical Y or" a separation of a compound represented by general FormulaA, above, separated from a compound represented by general Formula B, above, wherein the halogen atoms and the number of carbon atoms thereof are the same.

A further illustration stemming from the foregoing data is the eiiicient separation of l-chloron-octadecane from a mixture of the same and 2-chloro-n-hexadecane; or a mixture of the same and 2-chloro-n-cosane thus demonstrating the separation of a compound represented by general Formula A, above, from a compound represented by general Formula C:

wherein the sum or r-l-m is other than n-2, and wherein the halogen atom is the same as in (A).

As mentioned earlier, two parafin derivatives of the same chain length but having different substituents can be separated by plexation. This feature is illustrated by selective plexacl formation of l-chloro-n-octaue in a mixture containingthe latter and 2-bromo-n-octane. This may be ,referred to as the separation of a monohalide represented .by general Formula A from a monohalide represented by general Formula D:

wherein the sum of r-l-m is equal to n-Z, and wherein thehalogen atom X is different from X in A.

Still another separation which is effected readily is that of l-chloro-n-octane from a mixture containing the same and 2brornonheptane or a mixture of the same and Z-broino-n-nonane, that is, wherein the number of carbon atoms and the halogen atoms are diiierent. This is the separation of a compound represented by general Formula A from a compound represented by general Formula E:

wherein the sum of r-l-m is other than n-Z and wherein the halogen atoms X is different from X in A.

Among the various amines shown above are straight-chain secondary amines represented by general Formula F:

wherein R1 and R2 are n-alkyl groups or terminally-substituted n-alkyl groups, and wherein the total number of carbon atoms of R1 and R2 is at least about eight.

Amines of the type represented by (F) form strong pleXads with urea, in contrast with secondary amines in `which R1 and/or R2 are branched-chain alkyl groups or are other than terminally substituted alkyl groups; the latter amines have a much lower capacity to lform plexads with urea. For example, di(-n-butyl) amine, di(-n-amyl) amine, di -`ndecyl) amine, di(-dodecyl amine and di(-noctadecyl) amine readily formed plexads when agitated with a urea-saturated water solution at 25 C. In contrast, diZ-ethylhexyl) amine did not form a plexad under the same conditions. This difierencein behavior makes possible the preferential separation i of f straight-chain amines `from branched-chain amines such as are obtained in thereaction of primary and secondary alcohols,

or halides, with ammonia. This is illustrated by treating a mixture of di(-n-octyl) amine and di- (n-ethylhexyl) amine with a urea-saturated water solution at 25 C.; the di(-n-octyl) amine formed a plexad and the di( -2-ethylhexyl) amine did not.

Secondary amines represented by F are separated from tertiary amines of the character shown by general Formula G:

wherein R1, R2 and Ra are the same or diierent, straight-chain or branched-chain alkyl groups.

For example, under the conditions mentioned directly above, tri(nbutyl) amine failed to form a pleXad. Thus, secondary amines F are separated from tertiary amines G when contacted with urea. When a mixture of di (-n-butyl) amine and tri(n-butyl) amine is agitated with a saturated urea solution, di(-nbutyl) amine is selectively plexated. This procedure is particularly advantageous in separating amines obtained when ammonia is reacted with straight chain primary alcohols, particularly alcohols containing twelve or more carbon atoms, for in the latter case separation by distillatoin is difficult to effect Without concurrent decomposition of product.

(2) ANTIPLEX An antiplex, as defined above, is a compound incapable of forming a plexad with a pleXor, such as urea.

(3) PLExoR The plexor used herein solution in a singleor multiple-component solvent. This solution should range from partially saturated to supersaturated at the temperature at which it is contacted with a plexand or with a mixture containing one or more pleXands and antiplexes, and, in many cases, it will be found convenient to suspend a further supply of urea crystals in the solution, handling it as a slurry. For gravity or centrifugal separation, it is convenient to use a solvent of such a specic gravity that after the formation of a desired amount of plexad, the speciiic gravity of the solvent phase will be diierent from that of the plexad phase and of the antiplex phase to a degree suiiicient to permit separation by gravity, centrifuging, etc.

The solvent should be substantially inert to the plexand and to the compounds of the mixture and also to the urea. Preferably, it should also be heat stable, both alone and in contact with urea, at temperatures at which the desired plexad is not heat stable.

As indicated above, the solvent may be either singleor multiple-component. It is sometimes convenient, particularly Where the plexad is separated by gravity, to utilize a two-component system, as water and an alcohol, glycol, amine or diamine, and preferably a lower aliphatic alcolici euch as, methanol or ethanol, or a water-soluble amine such as piperidine. Such a solvent, partially saturated to supersaturated with urea, lends itself readily to a continuous process for separation by plexation.,V

Solutions containing sufiicientwater in orderV to minimize the solubility of the hydrocarbon deis urea, which is in aeenesc rivatives in the Vurea Vsolvent are often employed. The minimum quantity of water required in such instances depends upon the polarity and the inolecular weight of the hydrocarbon derivative, or plexand, being treated and, in general, this quam tity will be greater' with more polar plexands and with lower molecular weight compounds.

In certain cases the use of single-component solvents is advantageous. Single-compera nt solvents other than alcohols may be employed, al though they are normally not as useful as the lower aliphatic alcohols. Glycols may be eni ployed as single solvents, yet ethylene glycol isV generally not suitable in gravity separation operations vdus to high density of the ureasaturated solvent. The higher glycols parm ticularly the butylene glycols may be advantageously employed. Diamines such as die'- 'noethane, -propane and -butane may likewise be employed. Additional useful solvents formi-c acid, acetic acid, formamide and aoe'tonitrile, although the nrst three of these are subject to the same limitation as ethylene glycol.

Solvents generally useful when mixed with sufficient water, ethylene amine, to render them substantially insoluble in the derivatives being treated, are selected from the class of alcoholssuchas methanol, ethanol, propanol, etc.; others such as ethylene glycol di# methyl ether; and amines such as triethylamine, piperidine. When gravity separatic`^ is employed, the mixed solvent is preferable ject to the restriction that the density after saturation with urea mus be less than l.Il-l.l.

(il) TYPICAL SEPARA'rIoNs In order that this invention maybe more readily understood, typical separations are de scribed below with reference being made to the drawings attached hereto.

(a) Separation of piccanti from cumplen:

The procedure which may be employed in effecting the separation of terminally-substituted from non-terininally substituted, straight chain hydrocarbons may be essentially the same that described Yin copending application Serial lilo. 4,997, led January 29, 194:8. The pleiiand ob tained in decomposing the plexad obtained in a urea treatment of mixture of terminally-sub stituted and nonterminally-substituted straight chain hydrocarbons is very pure, provided the substituent group and the aliphatic chain length are of such dimensions that only the terminally-- substituted'hydrocarbon forms a plexad and provided theA plexad be carefully freed of occluded antiplex before it isdecomposed. For example, substantially pure l-halide is separated from the plexad obtained inthe treatment of terminallysubstituted and non-terminally-substituted chlorides or bromides of normal parafins containing from 8-16 carbon atoms.

In Figure l, a charge comprising a plexand and an antiplex, for example l-bromo-n-octane and 2bromo-noctane, respectively, enters through line I, to be contacted with urea'solution from line 2, and the charge and solution are intimately mixed in mixer 3. In case the charge undergoing treatment is rather viscousat the temperature of plexad (lbrornonoctaneurea) formation, it is advisable torprovide a diluent, such as for example, Va naphtha cut which may be recycled within the process, and described later, and joins include glycol or ethylene dil: r or,

' showing is diagrammatic, and that v settler Vintroduced by line 2l.

l2 the charge from line 4. Diluent make up is provided by line 5.

From mixer 3, wherein there is achievedl an intimate mixture of urea solution and chargatne mixture hows through line heat exchanger l, and cooler li into settler 9. There may be some or a good portion of plexad (lbromo-n-octane urea) formed in mixer but in general, it is preferred to operate mixer il at a temperature somewhat above thatv conducive to heavy formation of plexad. Then, in heat exchanger l, the temperature of the mixtureV is reduced, and in cooler adjusted, so that the desired plexad is formed. It will be recognized that this the heaterchangers and coolers, heaters, etc., shown will be of any type suitable, as determ- .ed by the physical characteristics of the materials being handled.

From cooler t, the plexadontaining mixture flows into settler ,9. This settler is preferably so managed that there is an upper phase of antiplex (2-bromo-n-octane), an intermediate phaseV of urea solution, anda lower region containing a slurry of plexad in the urea solution. The incoming mixture is preferably introduced into the solution phase, so lthat the antiplex 2 bromo-n-octane) may move upward and plexad downward, through some little distance in the solution, to permit adequate separation of plexad from antiplex and antiplex from plexad.

Antiplex will be removed from settler il by line l@ and introduced into fractionator Il, wherein the diluent is removed,l to pass overhead by vapor line I2 and eventually to use through line Il. Recovered antiplex (2-bromo-n-octane) passes from the system through line i3. Obviously if no diluent be used, fractionator II will be dispensed with. v Y

Plexad and urea solution, withdrawn from 9 through line Id, are passed through heat exchanger l and heater i5 to enter settler I through line Il. In this operation, the temperature is so adjusted that the plexand (l-bromo-n-octant) is freed from the plexad and, in settler It, the plexand rises to the top to be recovered from the system by means oi line El. The urea solution, thus reconstituted to its original condition by return to it o that portion of the urea which passed into plexad, is withdrawn from settler IE5 by line 2 and returned to process. Naturally, in a process of this kind there are minor mechanical and entrainment losses of urea solution, etc., and urea solution makeup is provided for by line IS. Y

In many cases, the separation of plexad and solution fromantiplex may be conducted with greater facility in a centrifuge operation. Such a setup is shown in Figure 2, wherein only the equivalent of that portion of Figure l centering about settler 9 is reproduced. Again in diagram form, the cooled mixture containing antiplex', plexad and urea solution enters centrifuge 20 through line 6. In many cases, it will be desirable to utilize a carrier liquid ink known manner in this operation and that liquid may be Antiplex will be carried olf through line I0, and plexad, urea solution, and carrier,` if present, pass through line 22 to a separation step, whichV may include washing and may be carried out in a settler, a filter, or another centrifugal operation, which separation is indicated diagrammatically at 23. Carrier liquid, if used, returns through line 2li, Vand urea solution and plexad pass through line I4. (Nora-line 6, I0 and I4 are the same lines,

1"`3 for the same functions, as in Figure `1 and are identically numbered.)

(b) Separation of one pleand from a second pleand In the case where both the terminally-substituted and non-terminally-substituted compounds form plexads, a concentration of the terminally-substituted compound will be obtained. The sharpness of separation of the terminallysubstituted compound will be greater, the greater the difference in the strength of the plexads formed with the two types of pure compounds. In general, this will be greater, the shorter the carbon chain length of parent hydrocarbon. For example, substantially pure l-bromo-n-octane can he obtained from a mixture with 2- bromo-n-octant in a single plexation. It is more diicult, however, to obtain separation between l-chloro-n-octadecane and Z-chloro-noctadecane. W The following serves to illustrate a procedure for `obtaining sharp separation between one plexand, 1chloronoctadecane, and a second plexand, 2-chloro-n-octadecane, the latter behaving as a secondary plexand in forming a plexad. This procedure is similar to a sweating or a solvent sweating procedure used in the rening of slack waxes, and is shown diagrammatically in Figure 3.

In Figure 3, a slurry of solid urea in a saturated urea solvent, which is preferably an aqueous alcoholic solution, is pumped from line 3| into a `turbomixer 32 where it is agitated with a mixture 1 and 2-ch1oro-n-octadecanes, which enter through line 33. An immiscible solvent charged through line 34 is also preferably employed, such as a light cut from a straight run naphtha in case the compounds of the mixture treated have: (l) a relatively high viscosity; (2) an appreciable solubility in the urea solvent; or (3) greater density than the urea solvent. The amount of excess solid urea employed should be suicient so that after the plexation is completed the urea solvent remains substantially saturated with urea.

Internal cooling means may be employed in 32 to further cool the mixture and remove the heat evolved during the plexation. The temperature employed in 32 will depend upon the chain length of the plexand and secondary plexand. If the chain length is such that it is not morethan `one or two carbon atoms greater than the minimum required to obtain plexation with the pure plexand at 25 C., then temperatures in the range of -l to 20 C. should be employed. If the chain length is from two to six carbon atoms greater than the minimum, temperature in the range of -30 C'. should be employed; and if the chain length is greater than six carbon atoms beyond the minimum, temperatures from 50 C. may be employed. It will be apparent, then, that conditions of operation vary considerably, conditions` selected being those appropriate for the formation of the desired plexad or plexads.

`The slurry of plexad, urea solvent and secondary plexand is pumped, by means of pump 36, through line 35 and cooler 3l wherein it may be further cooled if desired, and into gravity settler 38.

plus naphtha solvent rises to the top ,and-,is

In settler 38 the secondary plexand n-octadeca'ne, is removed as bottoms from fractionator 40 through line 4l. The naphtha solvent is taken from fractionator 4U through line 42, cooler 43, tank 44 and line 45 to be employed in solvent sweating zone 46. Naphtha solvent may also be recycled to fractionator 4!) through line 41, by means of pump 48.

In settler 38, theslurry of `plexadin urea solvent is taken off through line 49, heat exchanger 5l) and heater 5l into solvent sweating Zone (or mixer) 45. A portion of the clear urea solvent maybe removed from the center of 3B and recycled, through line 5| and pump 52,.t,oV mixer 32 if desired.

It is to be understood that the gravity settler 33 may be replaced by other separation means such. as a centrifuge or rotary filter, etc.

The mixture of solvent and plexad is heated 4 in solvent sweating zone 46 to a temperature sufcient to decompose the major portion of the plexad of the 2-chloro-n-octadecane, while preserving l the major portion of the plexad of l chloro n octadecane. The temperature employed in zone 46 isrelated to that employed in mixer 32, and will generally be maintained from 10-20o C. higher in zone 46 than in mixer 32.

The partially decomposed plexads, urea solvent, and. naphtha mixture is passed from zone 46 through line 53 to settler 54. The naphtha containing plexand, l-chloro-n-octadecane, and some secondary plexand, 2chloronoctadecane, is recycled through lines and 33 to mixer 32. The slurry of undecomposed plexad is withdrawn from the bottom of settler 54 through line 55, heat exchanger 5l, heater 53 into settler E9. The

vplexad is thus heated hot enough to cause complete decomposition or reversion of the plexads and solution of the urea in the urea solvent. Temperatures in the range of 55-85 C. are generally suitable.

Plexand, l-chloro-n-octadecane, contaminatedr with naphtha which has been occluded on the corresponding plexad (l-chloro-n-octadecaneurea) is withdrawn through line into fractionator S Naphtha is taken on" overhead from fractionator 6| through line 62, cooler 63, tank 64, pump and line t5, to mixer 3l. A portion of the naphtha may also be recycled to fractionator 6|` through line 6l. Plexand is recovered as bottoms through line B8.

Urea solution is recycled from the bottom of settler 59 through line 69, pump lll, heat ex-A changers 51 and 50, and line 5|.

Plexand of any desired purity may be obtained .l by either: (l) increasing the fraction of the total plexad decomposed in the solvent sweating zone 45), or (2) including a multiplicity of alternating solvent sweating zones (4t) and settling Zones (54) operated in series.

VI. ILLUSTRATIVE EXAMPLES The following examples serve to illustrate. and not in any sense limit, the present invention.

(a) TerminalZy-substituted straight chain paratns, general Formula` A general, the

experimentally is compared with the Vcorrelations given in Table IV. Table V is as follows:

16 80% methanol solution saturated with urea at 45 C. A plexad was formed and settled to the TABLE V.-COMPARISON OF MINIMUM CHAIN LENGTHS REQUIRED FOR UREA PLEXATION AT TALLY WITH THOSE IGIVEN IN TABLE II.V

C. FOR HYDROCARBONS-l DETERMINED EXPERIMEN- PLEXAD F0 Rl\IATIONALIPHATIC CHAIN LENGTH (b) Comparison of equilibrium values in the pexaticn of compounds of general Formulas A and B Piera-tion ci a plexand, dissolved in an antiplex such as a suitable branched chain hydrocarbon solvent, with a saturated urea solution proceeds until the concentration of the plexand is reduced to a certain minimum concentration which may be termed the equilibrium concentration. In equilibrium concentration is lower, the lower the temperature of plexation and is dependent only upon the temperature and not upon the solvent for the plexand, provided the urea solution is maintained saturated with urea and provided the plexand-solvent phase can be regarded as an ideal solution` Equilibrium Values were determined for several pairs of compounds, (A) and (B), by agitating solutions oi varying concentrations of the substituted hydrocarbon in iso-octane with a 70% methanol-% water solution saturated with urea Y and noting the minimum concentration required for plexad formation` The results are summarized in Table VI, below.

TABLE vI.-EQU1L1BRIUM VALUES 1N THE UREA PLEXATION oit HYDROCARBoN-l HYDROCAR- BON-2 PAIRs fir-- in Va single length are within theY be obtained be- A portion, parts by Volume,V

bottom of the urea solution. The upper layer, free of plexad, was decanted from the lower layer. The upper layer was distilled whereupon 2 methyl pentane was distilled off, and the composition oi thev bromide residue was determined by refractive index measurement.

The plexad was filtered from the urea solution, washed with 2-methyl pentane and then decomposed with water to urea and plexand. The recovered plexand was distilled to remove 2-methyl pentane and the residue was analyzed for the bromo-octanes by refractive index.

No Z-bromc-n-octane was removed from the original solution, while the bromo-n-octane content was reduced from 33.3 volume per cent to its equilibrium value, namely, 18.7 volume per cent.

VIII. UTILITY From the foregoing description, it'will be apparent that the invention has considerable application in theV chemical and related arts. For example, terminally sulfonated paramns may be separated from the non-terminally substituted Vin the chlorination of straight chain parains.

Also, in the high temperature, vapor-phase chlorination of olens, two principal products are produced, namely, the l-chloro-Z-olen and the 3-chloro-1-olefln according to the following representation:

The present method may be employed to eiect the separation between the foregoing l-chloro and the *3"chloro compounds.

The addition of a mercaptan or hydrogen bromide to a l-olen in the presence of air, oxygen or peroxides takes place with the addition of the mercapto radical, -SR, or bromo radical, -B1, to the terminal carbon atom of the olefin. If an olen mixture containing a straight chain l-olen is so treated, the derivatives obtained from the straight chain lolen can be selectively separated by urea plexation. The 1- olefin derivatives obtained in this manner may be used for various purposes, orV can be converted by known reactions to other useful products. For example, the bromide may be pyrolyzed to regenerate the pure l-olen. Y VNot only are the separation procedures contemplated herein useful for removing substantial amounts of a contaminating constituent, as an isomer or isomers, from a related compound, but they are of value when small or trace amounts of such an undesirable constituent are present.

In addition, the new plexads made available herein constitute desirable sources of urea and of the various plexands associated therewith. For example, the desired compounds can be kept in storage or shipped until just prior to use, when they are separated by reversion of the plexads.

Halogen compounds can be plexated from mixtures containing the same and form urea plexads, as described above and as described and claimed in application Serial No. 115,511, now abandoned. Sulfur-containing compounds are also plexated from their mixtures, and form plexads with urea, as described above and as described and claimed in application Serial No. 255,943, iiled November 13, 1951, as a continuation of application Serial No. 115,516 which has been abandoned. Plexation of compounds containing cyclic substituents, and urea plexads thereof, are described and are claimed in application Serial No. 116,593. Plexation with urea of various terminally substituted compounds from mixtures containing the same and non-terminally substituted compounds, described above, is also described and is claimed in application Serial No. 115,517.

Urea plexation of a non-terminally monosubstituted compound from mixtures containing the same and a non-terminally poly-substituted compound, is described and is claimed in application Serial No. 115,513, now U. S. Patent No. 2,642,422. Urea plexation of mixtures containing aliphatic compounds of different degrees of saturation is described and is claimed in application Serial No. 115,514; similarly, plexation of mixtures containing aliphatic hydrocarbons of difierent degrees of unsaturation and urea plexads of such hydrocarbons, are described and are claimed in application Serial No. 115,518, now U. S. Patent No. 2,642,423 and in divisional application thereof Serial No. 266,547, filed January 15, 1952.

Said applications Serial Nos. 115,511; 115,513; 115,514; 115,516 through 115,518 and 116,593 were iiled concurrently with this application on September 13, 1949.

Application Serial No. 374,707, filed August 17, 1953, is a continuation of said abandoned application Serial No. 115,511. Application Serial No. 407,197, led February 1, 1954, is a division of the instant application. And application Serial No. 410,573, filed February 16, 1954, is a 1S division of application Serial No. 266,547, filed January 15, 1952, which, in turn, is a division of said application Serial No. 115,518 (now Patent I claim:

l. The method for recovering a tertiary amine from a mixture containing the same and a secondary aliphatic amine in which the aliphatic groups are straight chains, in which the total number ci carbon atoms is at least eight and which consists of the elements carbon, hydrogen and nitrogen, which comprises: contacting said mixture with urea under conditions appropriate for the formation of a crystalline complex of urea and said secondary amine, whereupon said complex is formed and whereupon the said tertiary amine is unaiected by urea; separating the said complex from the remainder of the resulting reaction mixture; and recovering the said tertiary amine from the said remainder.

2. The method for recovering tri-(nabutyl.) amine from a mixture containing the same and di-(n-butyl) amine, which comprises: contacting said mixture with a urea-saturated water solution at 25 C., whereupon a crystalline complex of urea and di-(n-butyl) amine is formed and whereupon the said tri-(n-butyl) amine is unalected by urea; separating the said complex from the remainder of the resulting reaction mixture; and recovering the said tri-(n-butyl) amine from the said remainder.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Matignon: Bull Soc. Chim. Paris, vol. 37 1894), p. 575.

Baum: Ber deut. Chem, vol. 41 (1908), p.

528. Bengen: Reel 143 T. O. M., May 22, 1946, pp.

to 139. (Deposited Library of Congress.)

Bengen et al.: Experimentia, vol. 5, May 1949, p. 200. 

1. THE METHOD FOR RECOVERING A TERTIARY AMINE FROM A MIXTURE CONTAINING THE SAME AND A SECONDARY ALIPHATIC AMINE IN WHICH THE ALIPHATIC GROUPS ARE STRAIGHT CHAINS, IN WHICH THE TOTAL NUMBER OF CARBON ATOM IS AT LEAST EIGHT AND WHICH CONSISTS OF THE ELEMENTS CARBON, HYDROGEN AND NITROGEN, WHICH COMPRISES: CONTACTING SAID MIXTURE WITH UREA UNDER CONDITIONS APPROPRIATE FOR THE FORMATION OF A CRYSTALLINE COMPLEX OF UREA AND SAID SECONDARY AMINE, WHEREUPON SAID COMPLEX IS FORMED AND WHEREUPON THE SAID TERTIARY AMINE IS UNAFFECTED BY UREA; SEPARATING THE SAID COMPLEX FROM THE REMAINDER OF THE RESULTING REACTION MIXTURE; AND RECOVERING THE SAID TERTIARY AMINE FROM THE SAID REMAINDER. 